CN103881078B - Chlorination polypropylene carbonate and preparation method thereof - Google Patents

Abstract

The invention provides a kind of chlorination polypropylene carbonate and preparation method thereof, this chlorination polypropylene carbonate as shown in the formula (I).Compared with existing polypropylene carbonate, chlorination polypropylene carbonate is due to the existence of chlorine atom, make it have stronger electronegativity, the interaction of chlorination polypropylene carbonate and other polar materials can be strengthened, thus can be used as compatilizer, tackiness agent, coating, ink etc. and be widely used; Can make to produce interaction of hydrogen bond between chlorination polypropylene carbonate after introducing chlorine atom, and then its processing characteristics and mechanical property are all improved, and chlorine atom can improve the flame retardant properties of chlorination polypropylene carbonate material.

Description

Chlorinated poly(propylene carbonate) and its preparation method

technical field

The invention belongs to the technical field of polymer materials, and in particular relates to chlorinated poly(propylene carbonate) and a preparation method thereof.

Background technique

Carbon dioxide is an inexhaustible and cheap chemical raw material. The large-scale fixation of carbon dioxide into chemical materials has attracted increasing attention worldwide. Since Inoue and others used carbon dioxide and epoxy compounds to copolymerize high molecular weight aliphatic polycarbonates in 1969, the research on the copolymerization of carbon dioxide and epoxy compounds has been deepened and developed, and the use of carbon dioxide as raw materials to synthesize polymer materials has also become a polymer material. Research hotspots in the field of science. Polypropylene carbonate (PPC) is an alternating copolymer of carbon dioxide and propylene oxide, which is a biodegradable and environmentally friendly material.

At present, polypropylene carbonate (PPC), the copolymerization product of carbon dioxide and propylene oxide, has entered the stage of industrial production, but because its own glass transition temperature (Tg) is usually 30 ° C ~ 40 ° C, and it is amorphous, There are defects such as large low-temperature brittleness and poor high-temperature dimensional stability, and it is difficult to use it as a plastic alone. It is generally used as a modifier of rubber or plastic, which limits its wide promotion and application.

The Chinese patent whose publication number is CN1176269 discloses the modification method of aliphatic polycarbonate styrene-butadiene rubber, which can not only provide modified styrene-butadiene rubber with excellent heat resistance and mechanical properties, but also use cheap The aliphatic polycarbonate modified styrene-butadiene rubber, aliphatic polycarbonate is synthesized by carbon dioxide copolymerization, and the cost of the improved product is similar to that of pure styrene-butadiene rubber. The wide application of aliphatic carbonates can not only open up new resources and alleviate the shortage of chemical raw materials, but also have great significance for controlling the content of carbon dioxide in the atmosphere, alleviating the global greenhouse effect, and protecting the ecological environment.

The Chinese patent with publication number CN1436812A discloses a composite of polyhydroxyalkanoate and polypropylene carbonate. The compound is prepared by adding 100 parts by weight of one or more polyhydroxyalkanoates, 10 to 100 parts by weight of polypropylene carbonate, 10 to 100 parts by weight of plasticizer, and 1 to 3 parts by weight of antioxidant 1 to 4 parts by weight of the nucleating agent are firstly mixed, and then mixed and granulated at the melting temperature of polyhydroxyalkanoate. The composite combines the advantages of polyhydroxyalkanoate and polypropylene carbonate, improves the brittleness of polyhydroxyalkanoate, and has good comprehensive mechanical properties.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide chlorinated poly(propylene carbonate) and a preparation method thereof, and the chlorinated poly(propylene carbonate) is widely used.

The present invention provides a kind of chlorinated polypropylene carbonate shown in formula (I):

Wherein, x is an integer of 0 to 3; y is an integer of 0 to 2; n is the degree of polymerization.

Preferably, the n is 50-5000.

The present invention also provides a kind of preparation method of chlorinated polypropylene carbonate, comprising:

Mixing the poly(propylene carbonate) with the first dispersant, and reacting with chlorine gas to obtain the chlorinated poly(propylene carbonate) represented by the formula (I);

Wherein, x is an integer of 0 to 3; y is an integer of 0 to 2; n is the degree of polymerization.

Preferably, the mass ratio of the polypropylene carbonate to the dispersant is 100:(0.1-10).

The present invention also provides a kind of preparation method of chlorinated polypropylene carbonate, comprising:

Polypropylene carbonate is mixed with an organic solvent, and chlorine gas is introduced to react to obtain the chlorinated polypropylene carbonate shown in formula (I);

Wherein, x is an integer of 0 to 3; y is an integer of 0 to 2; n is the degree of polymerization.

Preferably, a first initiator is also included; the first initiator is selected from the group consisting of peroxides, azo compounds, tert-butyl perbenzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N , One or more of N-dimethyl-p-toluidine and N,N-bis(2-hydroxyethyl)-p-toluidine.

The present invention also provides a kind of preparation method of chlorinated polypropylene carbonate, comprising:

Mix polypropylene carbonate, emulsification accelerator, second dispersant with water, pass through chlorine gas to react, obtain the chlorinated polypropylene carbonate represented by formula (I);

Wherein, x is an integer of 0 to 3; y is an integer of 0 to 2; n is the degree of polymerization.

Preferably, a second initiator is also included; the second initiator is selected from the group consisting of sodium hydrogen peroxide nitrite system, ferrous hydrogen peroxide nitrate system, silver nitrate hydrogen peroxide system, sodium hydrogen peroxide bisulfite system, Ferrous ammonium hydrogen peroxide sulfate system, persulfate sulfite system, persulfate mercaptan system, dibenzoyl peroxide ferrous sulfate system, dibenzoyl peroxide system, dibenzoyl peroxide Acylthiol system, Dibenzoylthiol peroxide system, Ferrous lauryl sulfate peroxide system, Lauroyl formic acid peroxide system, Lauroylthiol peroxide system, Lauroylthiol peroxide system, Isopropyl Benzene hydroperoxide ferrous salt system, cumene hydroperoxide dihydroxyacetone system, cumene hydroperoxide derivative ferrous salt system, cumene hydroperoxide derivative dihydroxyacetone system, furan hydroperoxide One or more of ferrous salt system, furan hydroperoxide dihydroxyacetone system, tert-butyl hydroperoxide ferrous salt system and tert-butyl hydroperoxide dihydroxyacetone system.

Preferably, the emulsification accelerator is selected from one or more of polyoxyethylene fatty alcohol, polyoxyethylene alkylphenol and polyoxyethylene fatty alcohol ether.

Preferably, the mass ratio of the polypropylene carbonate, the emulsification accelerator and the second dispersant is 100:(0.1-10):(0.1-10).

The invention provides a chlorinated poly(propylene carbonate) and a preparation method thereof. The chlorinated poly(propylene carbonate) is represented by formula (I). Compared with the existing polypropylene carbonate, chlorinated polypropylene carbonate has stronger electronegativity due to the presence of chlorine atoms, which can enhance the interaction between chlorinated polypropylene carbonate and other polar materials, thereby It can be widely used as a compatibilizer, adhesive, coating, ink, etc.; after the introduction of chlorine atoms, hydrogen bond interactions can occur between chlorinated polypropylene carbonates, thereby improving its processing performance and mechanical properties. Improvement, and chlorine atoms can improve the flame retardancy of chlorinated polypropylene carbonate materials.

Description of drawings

Fig. 1 is the process flow diagram of the chlorinated poly(propylene carbonate) shown in solid-phase method preparation formula (I) of the present invention;

Fig. 2 is the process flow diagram of the chlorinated polypropylene carbonate shown in solution method preparation formula (I) of the present invention;

Fig. 3 is the process flow diagram of the chlorinated polypropylene carbonate shown in the preparation formula (I) of aqueous phase suspension method of the present invention;

Fig. 4 is the scanning electron microscope energy spectrum analysis spectrogram of the polypropylene carbonate used in the embodiment of the present invention 1;

Fig. 5 is a scanning electron microscope energy spectrum analysis spectrogram of the chlorinated poly(propylene carbonate) prepared in Example 1 of the present invention.

detailed description

The present invention provides a kind of chlorinated polypropylene carbonate shown in formula (I):

Wherein, x is an integer of 0-3, preferably an integer of 1-2; y is an integer of 0-2, preferably an integer of 1-2; n is a degree of polymerization, preferably 50-5000.

The present invention also provides a solid-phase preparation method of the chlorinated poly(propylene carbonate) represented by the above formula (I), comprising: mixing the poly(propylene carbonate) with the first dispersant, and reacting with chlorine gas to obtain the formula (I) Chlorinated poly(propylene carbonate) shown.

Among them, the present invention has no special limitation on the sources of all raw materials, which can be commercially available.

The first dispersant can be a dispersant well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably white carbon black; the polypropylene carbonate and the first dispersant are preferably in a mass ratio of 100 : (0.1-10) ratio mixing, more preferably 100: (0.5-6).

After mixing polypropylene carbonate with the first dispersant, chlorine gas is introduced to react to obtain chlorinated polypropylene carbonate represented by formula (I). The process flow chart of this solid-phase method is shown in Figure 1. Including the first dispersant and the first initiator. Wherein the molar ratio of chlorine to polypropylene carbonate is preferably (1-6):1; the temperature of the reaction is preferably -10°C to 100°C, more preferably 0°C to 80°C, and more preferably 10°C ~60°C; the reaction time is preferably 10-300 min, more preferably 50-200 min.

When the temperature of the reaction is lower than the glass transition temperature of polypropylene carbonate (30°C-40°C), it is preferable to add a first initiator, and the first initiator is preferably a peroxide, an azo compound, a peroxide One of tert-butyl benzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N,N-dimethyl-p-toluidine and N,N-di(2-hydroxyethyl)-p-toluidine One or more, more preferably a mixture of oxidizing initiators and reducing initiators, wherein the molar ratio of oxidizing initiators to reducing initiators is preferably greater than 1. The oxidizing initiator is preferably peroxide and/or tert-butyl perbenzoate, more preferably dibenzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide and benzene peroxide One or more of tert-butyl formate; the reducing oxidant is preferably N,N-dimethylaniline, N,N-dimethyl-p-toluidine and N,N-two (2-hydroxyethyl ) one or more of p-toluidine; the mass of the first initiator is preferably 0.01% to 5% of the mass of polypropylene carbonate, more preferably 0.1% to 5%.

When the temperature of the reaction is higher than the glass transition temperature of the carbonic acid ester, the first initiator may not be added, and it may react under the conditions of thermal initiation or ultraviolet light initiation; the first initiator may also be added to accelerate the reaction, Now the first initiator is preferably one or more of dibenzoyl peroxide, azobisisobutyronitrile and potassium persulfate; the quality of the first initiator is preferably 0.01% of the polypropylene carbonate quality % to 5%, more preferably 0.1% to 3%.

The present invention also provides another solution method for preparing the chlorinated poly(propylene carbonate) shown in the above formula (I), comprising: mixing poly(propylene carbonate) with an organic solvent, and introducing chlorine gas to react to obtain the formula (I) ) of chlorinated poly(propylene carbonate) shown.

Wherein, the organic solvent is an organic solvent that can dissolve polypropylene carbonate well known to those skilled in the art, and is not particularly limited, and is preferably carbon tetrachloride in the present invention; the quality of the polypropylene carbonate and The volume ratio of the organic solvent is preferably 1 g:(5-20) ml, more preferably 1 g:(8-15) ml.

After mixing polypropylene carbonate with an organic solvent, chlorine gas is introduced to react. Wherein the molar ratio of chlorine to polypropylene carbonate is preferably (1-6):1; the temperature of the reaction is preferably -10°C to 100°C, more preferably 0°C to 80°C, and more preferably 10°C ~60°C; the reaction time is preferably 10-300 min, more preferably 50-200 min.

When the temperature of the reaction is lower than the glass transition temperature of polypropylene carbonate (30°C-40°C), it is preferable to add a first initiator, and the first initiator is preferably a peroxide, an azo compound, a peroxide One of tert-butyl benzoate, potassium persulfate, sodium sulfite, N,N-dimethylaniline, N,N-dimethyl-p-toluidine and N,N-di(2-hydroxyethyl)-p-toluidine One or more, more preferably a mixture of oxidizing initiators and reducing initiators, wherein the molar ratio of oxidizing initiators to reducing initiators is preferably greater than 1. The oxidizing initiator is preferably peroxide and/or tert-butyl perbenzoate, more preferably dibenzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide and benzene peroxide One or more of tert-butyl formate; the reducing oxidant is preferably N,N-dimethylaniline, N,N-dimethyl-p-toluidine and N,N-two (2-hydroxyethyl ) one or more of p-toluidine; the mass of the first initiator is preferably 0.01% to 5% of the mass of polypropylene carbonate, more preferably 0.1% to 5%.

When the temperature of the reaction is higher than the glass transition temperature of the carbonic acid ester, the first initiator may not be added, and it may react under the conditions of thermal initiation or ultraviolet light initiation; the first initiator may also be added to accelerate the reaction, Now the first initiator is preferably one or more of dibenzoyl peroxide, azobisisobutyronitrile and potassium persulfate; the quality of the first initiator is preferably 0.01% of the polypropylene carbonate quality % to 5%, more preferably 0.1% to 3%.

After the reaction, the organic solvent is preferably removed and dried to obtain the chlorinated polypropylene carbonate represented by formula (I). The process flow diagram of the solution method is shown in Figure 2.

The present invention also provides a method for preparing chlorinated poly(propylene carbonate) represented by formula (I) by an aqueous phase suspension method, comprising: mixing poly(propylene carbonate), an emulsification accelerator, a second dispersant with water, and feeding chlorine gas to carry out Reaction, obtains the chlorinated polypropylene carbonate shown in formula (I).

Wherein, the emulsification accelerator is an emulsification accelerator well-known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably polyoxyethylene fatty alcohol, polyoxyethylene alkylphenol and polyoxyethylene fatty alcohol ether One or more of them; the second dispersant is a dispersant well known to those skilled in the art and there is no special limitation, preferably sodium polymethacrylate, polyvinylpyrrolidone, ethylene oxide in the present invention - one or more of the ethylene oxide copolymers; the mass ratio of the polypropylene carbonate, the emulsification accelerator and the second dispersant is preferably 100: (0.1-10): (0.1-10); The volume ratio of the mass of polypropylene carbonate to water is preferably 1:(10-30), more preferably 1:(15-25).

After mixing the polypropylene carbonate, the emulsification accelerator, and the second dispersant with water, it is preferable to further add the second initiator. The second initiator is preferably sodium hydrogen peroxide nitrite system, ferrous nitrate hydrogen peroxide system, silver nitrate hydrogen peroxide system, sodium bisulfite hydrogen peroxide system, ammonium ferrous sulfate hydrogen peroxide system, peroxide Sulfate sulfite system, persulfate thiol system, dibenzoyl peroxide ferrous sulfate system, dibenzoyl peroxide system, dibenzoyl peroxide thiol system, dibenzoyl peroxide Acylthiophenol system, lauroyl peroxide ferrous sulfate system, lauroyl formic acid peroxide system, lauroyl thiol peroxide system, lauroyl thiophenol peroxide system, cumene ferrous hydroperoxide system, Propylbenzene hydroperoxide dihydroxyacetone system, cumene hydroperoxide derivative ferrous salt system, cumene hydroperoxide derivative dihydroxyacetone system, furan hydroperoxide ferrous salt system, furan hydroperoxide di One or more in hydroxyacetone system, tert-butyl ferrous hydroperoxide system and tert-butyl hydroperoxide dihydroxyacetone system; the mass ratio of the second initiator to polypropylene carbonate is preferably ( 0.01-2): 100, more preferably (0.1-2): 100.

When the second initiator is not added, the reaction can be carried out under the conditions of thermal initiation or ultraviolet light initiation.

Chlorine gas is introduced for reaction, wherein the molar ratio of chlorine gas to polypropylene carbonate is preferably (1-6):1; the temperature of the reaction is preferably 4°C-80°C, more preferably 10°C-60°C , more preferably 30°C-60°C; the reaction time is preferably 10-300min, more preferably 50-200min.

After the reaction, it is preferred to add alcohols to precipitate the product, wash and dry to obtain the chlorinated polypropylene carbonate represented by formula (I), more preferably to add methanol to precipitate the product. At this time, the process flow chart of the aqueous phase suspension method is shown in Figure 3.

In order to further illustrate the present invention, a kind of chlorinated polypropylene carbonate provided by the present invention and its preparation method are described in detail below in conjunction with the examples.

The reagents used in the following examples are all commercially available.

Example 1

Add 100g of 60 mesh polypropylene carbonate (PPC) powder, 0.5g of a mixture of benzoyl peroxide and xylidine (the molar ratio of benzoyl peroxide to xylidine is 1.5:1) and 5g of white carbon black for reaction In the container, the temperature is gradually lowered under the condition of stirring in an ice-water bath. When the temperature is lower than 15 °C, chlorine gas is introduced. Before the temperature reaches 10 °C, the amount of chlorine gas introduced reaches 60% of the total amount of chlorine gas introduced. At 10°C, the amount of chlorine gas introduced reaches 95% of the total amount, and the last 5% of chlorine gas is introduced when the temperature drops to 5°C. The total amount of chlorine gas introduced is 240g, and the reaction is carried out for 2 hours, and then the reaction bottle is driven away with clean air In the residual chlorine, the chlorine content of 9% white powdery chlorinated poly(propylene carbonate) was obtained.

The polypropylene carbonate silicon wafer coating film used in Example 1 was analyzed by a scanning electron microscope to obtain its scanning electron microscope energy spectrum analysis spectrum, as shown in FIG. 4 .

The chlorinated poly(propylene carbonate) silicon wafer coating film obtained in Example 1 was analyzed by a scanning electron microscope to obtain its scanning electron microscope energy spectrum analysis spectrum, as shown in FIG. 5 .

After coating the polypropylene carbonate silicon wafer used in Example 1, the water contact angle test was carried out, and the contact angle obtained was 90°.

Carry out water contact angle test after the chlorinated poly(propylene carbonate) silicon sheet coating film obtained in embodiment 1, obtain its contact angle and be 65 °, illustrate that the polarity of chlorinated poly(propylene carbonate) increases compared with polypropylene carbonate .

Example 2

Add 100g of 60-mesh polypropylene carbonate (PPC) powder into the reactor, gradually lower the temperature in an ice-water bath, then add 0.3g of a mixture of benzoyl peroxide and xylidine (the moles of benzoyl peroxide and xylene The ratio is 1.5:1) and 5g white carbon black, feed chlorine gas, and then gradually bring to room temperature, the total amount of chlorine gas introduced is 240g, react for 2h, then use clean air to drive away the residual chlorine gas in the reaction bottle, and the chlorine content is 12% Chlorinated Polypropylene Carbonate in white powder form.

Example 3

Add 100g of 60-mesh polypropylene carbonate (PPC) powder, 0.4g of benzoyl peroxide and 5g of white carbon black into the reactor, feed chlorine gas, raise the temperature to 55°C, the total amount of chlorine gas introduced is 240g, and react for 2 hours. Then use clean air to drive away the residual chlorine in the reaction bottle to obtain a white powdery chlorinated polypropylene carbonate with a chlorine content of 24%.

Example 4

Add 100g of 60-mesh polypropylene carbonate (PPC) powder and 5g of white carbon black into the reactor, pass chlorine gas under the irradiation of ultraviolet light, raise the temperature to 30°C, the total amount of chlorine gas introduced is 240g, react for 2h, and then use The clean air drives away the residual chlorine in the reaction bottle to obtain a white powdery chlorinated polypropylene carbonate with a chlorine content of 9%.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. the chlorination polypropylene carbonate shown in a formula (I):

Wherein, x is the integer of 0 ~ 3; Y is the integer of 0 ~ 2; N is the polymerization degree.

2. chlorination polypropylene carbonate according to claim 1, is characterized in that, described n is 50 ~ 5000.

3. a preparation method for chlorination polypropylene carbonate, is characterized in that, comprising:

By polypropylene carbonate and the first dispersant, pass into chlorine and react, obtain the chlorination polypropylene carbonate shown in formula (I);

Wherein, x is the integer of 0 ~ 3; Y is the integer of 0 ~ 2; N is the polymerization degree.

4. preparation method according to claim 3, is characterized in that, the mass ratio of described polypropylene carbonate and the first dispersion agent is 100:(0.1 ~ 10).

5. a preparation method for chlorination polypropylene carbonate, is characterized in that, comprising:

Polypropylene carbonate is mixed with organic solvent, passes into chlorine and react, obtain the chlorination polypropylene carbonate shown in formula (I);

Wherein, x is the integer of 0 ~ 3; Y is the integer of 0 ~ 2; N is the polymerization degree.

6. according to claim 3 or preparation method according to claim 5, it is characterized in that, also comprise the first initiator; Described first initiator is selected from superoxide, azo-based compound, t-butylperoxyl benzoate, Potassium Persulphate, S-WAT, N, accelerine, N, one or more in N-dimethyl-p-toluidine and N, N-bis-(2-hydroxyethyl) para-totuidine.

7. a preparation method for chlorination polypropylene carbonate, is characterized in that, comprising:

Polypropylene carbonate, emulsification promoter, the second dispersion agent are mixed with water, passes into chlorine and react, obtain the chlorination polypropylene carbonate shown in formula (I);

Wherein, x is the integer of 0 ~ 3; Y is the integer of 0 ~ 2; N is the polymerization degree.

8. preparation method according to claim 7, is characterized in that, also comprises the second initiator, described second initiator is selected from hydrogen peroxide Sodium Nitrite system, hydrogen peroxide Iron nitrate system, hydrogen peroxide Silver Nitrate system, hydrogen peroxide sodium hydrogen sulfite system, hydrogen peroxide ferrous ammonium sulphate system, persulphate sulphite system, persulphate thiol, dibenzoyl peroxide ferrous sulfate salt system, dibenzoyl peroxide formic acid system, dibenzoyl peroxide thiol, dibenzoyl peroxide thiophenol system, lauroyl peroxide ferrous sulfate salt system, lauroyl peroxide formic acid system, lauroyl peroxide thiol, lauroyl peroxide thiophenol system, isopropyl benzene hydroperoxide ferrous salt system, isopropyl benzene hydroperoxide otan system, isopropyl benzene hydroperoxide derivative ferrous salt system, isopropyl benzene hydroperoxide derivative otan system, furans hydrogen peroxide ferrous salt system, furans hydrogen peroxide otan system, one or more in tertbutyl peroxide ferrous salt system and tertbutyl peroxide otan system.

9. preparation method according to claim 7, is characterized in that, described emulsification promoter be selected from polyoxyethylene fatty alcohol, polyoxyethylene alkylphenol and polyoxyethylene aliphatic alcohol ether one or more.

10. preparation method according to claim 7, is characterized in that, the mass ratio of described polypropylene carbonate, emulsification promoter and the second dispersion agent is 100:(0.1 ~ 10): (0.1 ~ 10).